Activator for oxygen baths



Patented Oct. 17, 1939 UNITED sTATEs ACTIVATOR FOR OXYGEN BATHS Richard Neu, Dessau-Rosslau, Anhalt, Germany,

assignor, by mesne assignments, to Unichem Chemikalien Handels A.-G., Zurich, Switzerland, a corporation of Switzerland N6 Drawing. Application January 15, 1937, Se-

rial No. 120,715. In Germany January 15,.

1936 a '5' Claims.

It is known that certain metals or metal salts respectively made of peroxides, perborates, persulfates, percarbonates and the like are able of liberating the bound oxygen. For this purpose there are in first line the salts 'ofcopper, manganese, nickel, cobalt, iron and silver to be considered, either alone or in combination with or- Moreover the bath, by the precipitation of tinged metal-hydroxides grows mean-looking and turbid', the flaky precipitate' deposits itself on the body of the bathing person and causesa soiling and damaging of the bath-towels. With certain catalysers the development of oxygen goes on so slowly that the liberating of the, oxygen takes several hours. Certain other catalysers which, at the contrary, cause a very strong development of oxygen, show the drawback that they decompose also themselves during the gas-development While separating metal-hydroxides or metal oxy-hydrates respectively, so that the bath becomes mean-looking. Among the compounds of the aforedescribed kind there are the heavy metal salts of sulfonated" fatty stufis and particularly of fatty alcohols. Those metal salts distinguish themselves e. g. by not letting so easily escape i the oxygen from the surface of the bath-liquid, if

they areadded to the perborate, i. e. by retaining it in a stiff froth-cover which even after complete decomposition of the perborate persists for a good while, allowing thus a perfect utilization or respectively, the salts of those organic sulfuric acid derivatives with amines into water-soluble complex compounds. In the mentioned formula R means any higher molecular hydrocarbon resi- 55 due of no less than 6 to 30 carbon atoms, X means the atoms or atom groups S, 0, COO, OCO, NR",

S02, NR"SO2, CONR" and the like or it may be left out, whereas R means an alkylen residue eventually substituted by hydroxylor halogengroups or, if Y be absent, also an arylen residue;

of the oxygen. Attempts had already been made I R means hydrogen or any hydrocarbon residue, Y means sulfur or oxygen or it may be absent, and n represents the numbers 1 or 2. As sulfuric acid derivatives of higher molecular organic compounds of the above formula the following compounds may be cited: the sulfuric acid ester of the dodecyl-alcohol, the sulfuric acid ester of the selachyl-alcohol, the w-butylether of the decyl-w-sulfuric acid ester, the sulfuric acid ester of the 1,10-decandiol-monoacetate, the w-hexyl-thio-ether of the hexylthio-sulfuric acidester, the w-sulfuric acid ester of the caprilic acid-butyl-amide, the w-sulfuric acid ester of the decansulfonic acid phenyl amide, the (ii-sulfuric acid ester of the ricinolic alcohol, 'further thew-laurylor, respectively, the naphthenyl ether of the ethane-sulfonic acid, the w-butylor, respectively, the cyclohexyl ether of the decan-l-sulfonic acid, the o-phenyl-thiohexane sulfonic acid, the cetyl-thio-ethane sulfonic acid, the dodecyl-sulfonic ethane sulfonic acid, the N-lauryl-amido-ethane "sulfonicacid, the N-dioctyl-acetic-amide sulfonic acid, the N,N-dodecyl-p-toluol-sulfonyl amido-ethane su'lfonic acid, the oleic acid ester of the hydroxyethane sulfonic acid, the N-cetyl sulfonic sulfanilic'acid, the naphthenic acid amide of the amide-ethane sulfonic acid, the w-phenyldecan sulfonic acid. v

As heavy metal salts to be employed to form 'the heavy 'metal salts from the sulfuric acid derivatives of the higher molecular organic compounds, the following inorganic or organic salts may becitedz' the chlorides, nitrates, sulfates, acetates etc. of the copper, manganese, nickel, cobalt, iron and.silver etc.

For the converting with the above mentioned organic sulfuric-acid derivatives there are in first line the alkylamines, the hydroxy-alkylamines, amino alcohols or their ethers, aminoalkyl-polyalcohols, amino-alkyl-thiolsetc. to be considered. But under certain circumstances also cyclic amines may beapplied. Thus the following amines are to be considered: propylamine, tri-ethyl-amine, benzyl-amine, mono-diand tri-ethanol-amine, hydroxy-benzyl-amine, ethoxy-ethyl-amine, tri-ethoxy-tri-ethyl-amine, glucamine, pp-diamino-diethyl-sulfide, l-amino-ethane-thiol, cyclohexyl-amine, pyridine, piperidine, methyl-piperidine, aniline and the like. 7

The advantages of the new oxygen-deiielo'pers v consist, on the one hand, in a quiet and uniform gas-developing from peroxides or per-salts in aqueous baths, without any decomposition of the latter and without precipitating any metal compounds. Furthermore, owing to the froth formed during the gas-development there occurs no or' but a very slow escaping of the liberated oxygen, so that its perfect utilization is .secured while the treatment of single body-parts is practicable without ado. Moreover one needs comparatively little amounts of water to prepare the oxygen baths, as the froth-cover, owing to the formation of oxygen-bearing froth-bubbles, may be brought'in direct contact with the body-surface.

The claimed complex compounds maybe produced and applied either in a solid or in a dissolved form.

' Example 1 21X weight parts of sodium salt of the dodecylsulfuric acid ester are dissolved in ethyl-alcohol while ,warming, whereupon they are mixed with an aqueous solutionyconcentrated as much aspossible, of 12.5 weight parts of copper-sulfate. Now by heating for some time-a greenish substance is precipitated, which after an addition of 45- weight parts of triethyl-amine dissolves itself in forming a dark-blue solution. This solution is then concentrated in vacuo and mixed and pulverized with sodium tetraborate, sodium sulfate, sodium chloride or with other salts, eventually in adding some perfumes. The thus resuiting light-green powder gives a clear solution Example 2 The condensation-product obtainable in the usual way from 30weight parts of ,oleic acid chloride and 14 weight parts "of methyl-taurin, is changed over into the barium salt and mixed in the warmth to form a concentrated aqueous solution with 28 weight parts of cobalt sulfate cohols, amino alkyl thiols,. and cyclic amines, with a salt of a heavy metal selected from the group which consists of the metals copper, manganese, nickel, cobalt, iron, and silver; said salt being a sulfuric acid derivative of an organic compound of high molecular weight having the 9 general formula:

R-XL-R (YIr-SO3H) n wherein R represents a high molecular weight hydrocarbon radical containing from 6 to 30 carbon atoms; X represents a radical selected from the group which consists of S, O, COO,

resents a radical selected from the group which consists of hydrogen and hydrocarbon radicals; Y represents a radical selected from the group which consists of sulfur and oxygen; n represents a number selected from the group which consists of 1 and 2; and;-L represents a number selected from the group which consists of 0 and 1. 2. An activator for oxygen baths comprising a complex compound of the copper salt of the dodecyl-sulfuric=acid ester with tri-ethyl-amine. 3. An activator for oxygen baths comprising a complex compound of the manganese salt of the glycero-mon0-dodecyl-sulfuric acid ester with tri-ethanol-amine.

4. An activator for oxygen baths comprising a complex compound of the cobalt salt of the dissolved in60 weight parts of water. The precipitating barium-sulfate is filtered off and the clear filtrate is concentrated in vacuo to about half its volume The obtainable aqueous concentrate of the cobalt salt of the oleyl-methylamido ethane sulfonic acid is then mixed with 27.5 weight parts of -y-amino-a,fi-propylen-glycol, whereupon it is slightly warmed until complete solution and then concentrated in vacuo. After cooling the dry complex cobalt compound may eventually be mixed with salts as indicated imExampie 1.

Instead of the cobalt salt of the oleyl-methylamido-ethane sulfonic acid the salts of the 'cetylsulfonic acid, of the lauroyl-hydroxy-ethane sulfonic acid or of the a-dodecyl-ether of the p -hy- I droxy-propane-v-sulfonic acid of metals forming complex compounds, may in the same way be converted with amines.

By means of the aforesaid developers for oxygen-baths it is possible practically to decompose unlimited amounts of peroxides or persalts in aqueous baths.

I claim: 1

1. An activator for a bath containing active oleyl-methyl-amido-ethane sulfonic acid -amino-a,p-propylen-glycol.

5, A bleaching bath comprising an aqueous solution of an active oxygen-yielding compound selected from the group which consists of peroxides, perborates, persulfates, and percarbonates which contains, as an additional ingredient, an activator which comprises a product result ing from the reaction of an amine selected from the. group which consists of alkyl amines, hydroxy alkyl amines, amino alcohols, ethers of amino alcohols, amino alkyl poly alcohols, amino alkyl thiols, and cyclic amines; with a salt of a heavy metal selected from the group which consists of the metals copper, manganese, nickel, cobalt, iron, and silver, said salt being a sulfuric with "acid derivative of an organic compound of high molecular weight having the general formula: RxLR'(YLsO:H)n

wherein R represents a high molecular weight hydrocarbon radical containing from 6 to 30 carbon atoms; X represents a radical selected a from the group which consists of S. 0, C00;

000, NR", S02, NR"SO2, and CONR"; R represents a radical selected from the group which consists of the alkylene radicals, hydroxyl sub stituted all-xylene radicals, halogen substituted oxygen-yielding "compounds which comprises a product resulting from the reaction of an amine selected from the group whichconsists of alkyl amines, hydroxy alkyl amines, amino alcohols, ethers of amino alcohols, amino alkyl-poly alalkylene radicals, and arylene radicals; R" represents a radical selected from the group which consists of hydrogen and hydrocarbon radicals;

Y represents a radicalselected from the group' which consists of sulfur and oxygen; n represents-a number selected from the group which 

